US3808273A - Process for the production of alkylated n,n'-diphenyloxamides - Google Patents
Process for the production of alkylated n,n'-diphenyloxamides Download PDFInfo
- Publication number
- US3808273A US3808273A US00170660A US17066071A US3808273A US 3808273 A US3808273 A US 3808273A US 00170660 A US00170660 A US 00170660A US 17066071 A US17066071 A US 17066071A US 3808273 A US3808273 A US 3808273A
- Authority
- US
- United States
- Prior art keywords
- diphenyloxamide
- methyl
- ethyl
- tert
- ethoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 title description 39
- 230000008569 process Effects 0.000 title description 28
- -1 HYDROXYL GROUPS Chemical group 0.000 abstract description 65
- 150000001875 compounds Chemical class 0.000 abstract description 24
- 230000005855 radiation Effects 0.000 abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011368 organic material Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 239000001117 sulphuric acid Substances 0.000 description 20
- 235000011149 sulphuric acid Nutrition 0.000 description 20
- 239000000463 material Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 13
- 239000007858 starting material Substances 0.000 description 12
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 229940100198 alkylating agent Drugs 0.000 description 7
- 239000002168 alkylating agent Substances 0.000 description 7
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229960004592 isopropanol Drugs 0.000 description 5
- 150000003138 primary alcohols Chemical class 0.000 description 5
- 150000003333 secondary alcohols Chemical class 0.000 description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 5
- 150000003509 tertiary alcohols Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- FRDAATYAJDYRNW-UHFFFAOYSA-N 3-methyl-3-pentanol Chemical compound CCC(C)(O)CC FRDAATYAJDYRNW-UHFFFAOYSA-N 0.000 description 4
- MJOKZMZDONULOD-UHFFFAOYSA-N 3-methyloctan-4-ol Chemical compound CCCCC(O)C(C)CC MJOKZMZDONULOD-UHFFFAOYSA-N 0.000 description 4
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 4
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- RYKIMYINWPEUBW-UHFFFAOYSA-N n',n'-diphenyloxamide Chemical class C=1C=CC=CC=1N(C(=O)C(=O)N)C1=CC=CC=C1 RYKIMYINWPEUBW-UHFFFAOYSA-N 0.000 description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003223 protective agent Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical class NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- JWJJUASADIJNCF-UHFFFAOYSA-N n'-ethoxy-n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1N(OCC)C(=O)C(=O)NC1=CC=CC=C1 JWJJUASADIJNCF-UHFFFAOYSA-N 0.000 description 3
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical class C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LGAQJENWWYGFSN-PLNGDYQASA-N (z)-4-methylpent-2-ene Chemical compound C\C=C/C(C)C LGAQJENWWYGFSN-PLNGDYQASA-N 0.000 description 2
- PFHLGQKVKALLMD-UHFFFAOYSA-N 2,2-dimethylhexan-3-ol Chemical compound CCCC(O)C(C)(C)C PFHLGQKVKALLMD-UHFFFAOYSA-N 0.000 description 2
- PLSMHHUFDLYURK-UHFFFAOYSA-N 2,3,4-trimethyl-3-pentanol Chemical compound CC(C)C(C)(O)C(C)C PLSMHHUFDLYURK-UHFFFAOYSA-N 0.000 description 2
- DRHABPMHZRIRAH-UHFFFAOYSA-N 2,4,4,6,6-pentamethylhept-2-ene Chemical group CC(C)=CC(C)(C)CC(C)(C)C DRHABPMHZRIRAH-UHFFFAOYSA-N 0.000 description 2
- FMLSQAUAAGVTJO-UHFFFAOYSA-N 2,4-dimethylpentan-2-ol Chemical compound CC(C)CC(C)(C)O FMLSQAUAAGVTJO-UHFFFAOYSA-N 0.000 description 2
- LFEHSRSSAGQWNI-UHFFFAOYSA-N 2,6,8-trimethylnonan-4-ol Chemical compound CC(C)CC(C)CC(O)CC(C)C LFEHSRSSAGQWNI-UHFFFAOYSA-N 0.000 description 2
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 2
- WFRBDWRZVBPBDO-UHFFFAOYSA-N 2-methyl-2-pentanol Chemical compound CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 description 2
- ISTJMQSHILQAEC-UHFFFAOYSA-N 2-methyl-3-pentanol Chemical compound CCC(O)C(C)C ISTJMQSHILQAEC-UHFFFAOYSA-N 0.000 description 2
- KBCNUEXDHWDIFX-UHFFFAOYSA-N 2-methyloctan-2-ol Chemical compound CCCCCCC(C)(C)O KBCNUEXDHWDIFX-UHFFFAOYSA-N 0.000 description 2
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 2
- FJXOYCIYKQJAAF-UHFFFAOYSA-N 3,4-dimethylhexan-3-ol Chemical compound CCC(C)C(C)(O)CC FJXOYCIYKQJAAF-UHFFFAOYSA-N 0.000 description 2
- NPHCXUPGMINOPP-UHFFFAOYSA-N 3,6-dimethyloctan-3-ol Chemical compound CCC(C)CCC(C)(O)CC NPHCXUPGMINOPP-UHFFFAOYSA-N 0.000 description 2
- KYWJZCSJMOILIZ-UHFFFAOYSA-N 3-methylhexan-3-ol Chemical compound CCCC(C)(O)CC KYWJZCSJMOILIZ-UHFFFAOYSA-N 0.000 description 2
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 2
- GDCOAKPWVJCNGI-UHFFFAOYSA-N 4-methylnonan-4-ol Chemical compound CCCCCC(C)(O)CCC GDCOAKPWVJCNGI-UHFFFAOYSA-N 0.000 description 2
- FCOUHTHQYOMLJT-UHFFFAOYSA-N 6-methylheptan-2-ol Chemical compound CC(C)CCCC(C)O FCOUHTHQYOMLJT-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- HVYDMYVCFZRHNQ-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n'-(2-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1N(C(=O)C(N)=O)C1=CC=CC=C1CC HVYDMYVCFZRHNQ-UHFFFAOYSA-N 0.000 description 2
- YIMHRDBSVCPJOV-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-(2-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1CC YIMHRDBSVCPJOV-UHFFFAOYSA-N 0.000 description 2
- FCBBRODPXVPZAH-UHFFFAOYSA-N nonan-5-ol Chemical compound CCCCC(O)CCCC FCBBRODPXVPZAH-UHFFFAOYSA-N 0.000 description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N octan-4-ol Chemical compound CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- VVCFYASOGFVJFN-UHFFFAOYSA-N 2,4-Dimethyl-2-pentene Chemical compound CC(C)C=C(C)C VVCFYASOGFVJFN-UHFFFAOYSA-N 0.000 description 1
- KRIMXCDMVRMCTC-UHFFFAOYSA-N 2-methylhexan-2-ol Chemical compound CCCCC(C)(C)O KRIMXCDMVRMCTC-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- RITONZMLZWYPHW-UHFFFAOYSA-N 3-methylhex-1-ene Chemical compound CCCC(C)C=C RITONZMLZWYPHW-UHFFFAOYSA-N 0.000 description 1
- RYKZRKKEYSRDNF-UHFFFAOYSA-N 3-methylidenepentane Chemical compound CCC(=C)CC RYKZRKKEYSRDNF-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- BOJLCKCCKQMGKD-UHFFFAOYSA-N 4-ethylhexan-3-ol Chemical compound CCC(O)C(CC)CC BOJLCKCCKQMGKD-UHFFFAOYSA-N 0.000 description 1
- RGCZULIFYUPTAR-UHFFFAOYSA-N 5-Methylhexan-3-ol Chemical compound CCC(O)CC(C)C RGCZULIFYUPTAR-UHFFFAOYSA-N 0.000 description 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- IEFHRYGAIIQOBP-UHFFFAOYSA-N N'-(2-hydroxyphenyl)-N-phenyloxamide Chemical compound OC1=C(C=CC=C1)NC(=O)C(=O)NC1=CC=CC=C1 IEFHRYGAIIQOBP-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001756 Polyvinyl chloride acetate Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- ZQDPJFUHLCOCRG-WAYWQWQTSA-N cis-3-hexene Chemical compound CC\C=C/CC ZQDPJFUHLCOCRG-WAYWQWQTSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 235000014541 cooking fats Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WCYAALZQFZMMOM-UHFFFAOYSA-N methanol;sulfuric acid Chemical compound OC.OS(O)(=O)=O WCYAALZQFZMMOM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PJLHXGJEENSOBG-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-phenyloxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1 PJLHXGJEENSOBG-UHFFFAOYSA-N 0.000 description 1
- KWKRTNFTBCZAGB-UHFFFAOYSA-N n'-phenyloxamide Chemical class NC(=O)C(=O)NC1=CC=CC=C1 KWKRTNFTBCZAGB-UHFFFAOYSA-N 0.000 description 1
- SZDYLESNAGYCAH-UHFFFAOYSA-N n-(2-ethylphenyl)-n'-(2-hydroxyphenyl)oxamide Chemical compound CCC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1O SZDYLESNAGYCAH-UHFFFAOYSA-N 0.000 description 1
- OZFTWWJTWRRNDX-UHFFFAOYSA-N n-(2-ethylphenyl)-n'-(2-octoxyphenyl)oxamide Chemical compound CCCCCCCCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1CC OZFTWWJTWRRNDX-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- QXYWIOWTBOREMG-UHFFFAOYSA-N nonadecan-2-ol Chemical compound CCCCCCCCCCCCCCCCCC(C)O QXYWIOWTBOREMG-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/42—Amides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
- C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
- C09K15/22—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen containing an amide or imide moiety
Definitions
- This invention relates to a process for the production of the alkylated N,N'-diphenyloxamides of formula @NH-C o-c -NH- A in which 1 to 4 secondary or tertiary alkyl radicals having 3 to 20 carbon atoms are bound to the nuclei A and/ or B and the nuclei A and B may additionally contain hydroxyl groups and/or hydrocarbon radicals having 1 to 20 carbon atoms which may be bound through oxygen or sulphur atoms. These compounds absorb ultraviolet rays and protect light-sensitive organic materials, notably plastics, from the detrimental action of this radiation.
- This invention relates to a process for the production of alkylated N,N'-diphenyloxamides of the formula in which 1 to 4 secondary or tertiary alkyl radicals having 3 to 20 carbon atoms are bound to the nuclei A and/or B and the nuclei A and B may additionally contain hydroxyl groups and/or hydrocarbon radicals having 1 to 20 carbon atoms which may be bound through oxygen or sulphur atoms.
- This new process is characterized by the alkylation, in the presence of sulphuric acid, of 1 mol of a compound of the formula in which the nuclei A and/or B may contain hydroxyl groups and/or hydrocarbon radicals having 1 to 20 carbon atoms which may be bound through oxygen or sulphur atoms, with 1 to 4 mols of an olefin having 3 to 20 carbon atoms, or a secondary or tertiary alcohol.
- N,N-diphenyloxamides alkylated in the nucleus are obtained in very good yield. This is surprising since in the analogous reaction of other N-phenylamides, for example N-phenylacetamide, no or very little nucleoalkylated amide is obtained. The dilference is probably due to the fact that the amides of Formula II, in contrast to other amides such as N-phenylacetamide, are stable under the reaction conditions.
- Each of the nuclei A and B in the General Formula II may be unsubstituted or substituted.
- the following substituents are suitable: the hydroxyl group, which preferably occurs only once in a benzene nucleus, straight or branched alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert.
- cycloalkyl radicals such as the cyclohexyl radical, aryl radicals, in particular phenyl, aralkyl radicals such as the benzyl radical, alkoxy radicals such as methoxy, ethoxy, iso-propoxy, n-butoxy, nhexoxy, n-octoxy, dodecyloxy and octadecyloxy, alkylmercapto radicals such as methylmercapto, ethylmercapto,
- the preferred substitutents on the nuclei A and B of the starting compounds of Formula II are hydroxyl groups, alkyl groups having 1 to 4 carbon atoms and alkoxy and alkylmercapto groups having 1 to 8 carbon atoms.
- the alkylating agent may be chosen from the following: propene, l-butene, Z-butene, iso-butylene, 2-methyll-butene, 2-methyl-2-butene, 3-methyl-l-butene, l-pentene, Z-ethyl-l-butene, 3,3-dimethyl-l-butene, l-hexene, 3- methyl-l-pentene, 4 methyl-2-pentene, 2,4-dirnethyl-2- pentene, 4,4-dimethyl 1 pentene, 2-heptene, 3-methyll-hexene, tripropylene, tetrapropylene, di-iso-butylene, triiso-butylene, l-hexadecene, l-heptadecene, l-octadecene, l-eicosene, iso-propanol, secondary butanol, tertiary
- the olefins and the secondary or tertiary alcohols containing 3 to 12 or more, especially 3 to 9, carbon atoms are given preference as alkylating agents so that the final products of Formula I bear preferably 1 to 4 secondary or tertiary alkyl radicals having 3 to 12 or in particular 3 to 9 carbon atoms.
- sulphuric acid is used both as catalyst and as condensing agent. In order to be sufficiently effective it must be employed in highly concentrated form, i.e. of more than preferably -100% strength. Very low percentage oleum containing e.g. up to 5% sulphur trioxide, is also suitable. In order to prevent the decomposing action of the sulphuric acid on the 0xamides to the greatest possible extent, it is advisable to dampen the activity of the acid by adding a diluent such as formamide, dimethyl formamide, ammonium sulphate, or one of the sulphates of alkylamines or primary alcohols.
- a diluent such as formamide, dimethyl formamide, ammonium sulphate, or one of the sulphates of alkylamines or primary alcohols.
- a highly suitable diluent or damping agent of this type is methanol, which is converted into methylsulphuric acid by sulphuric acid.
- methanol which is converted into methylsulphuric acid by sulphuric acid.
- secondary or tertiary alcohols are employed as alkylating agents, water is split off in the reaction; it is therefore advisable to slowly add additional sulphuric acid in the course of the reaction so that the freed water does not dilute the sulphuric acid too heavily. It is best to choose the amount and the concentration of sulphuric acid so that its total water content at the end of the reaction (from the methanol present, when used, and/or from the alcohol used for alkylating) does not exceed 15%.
- oleum it is advisable to set the reaction mixture with a diluent, e.g. a primary alcohol such as methanol, in a quantity sufficient to preclude sulphonation of the diphenyl oxamide. If it is desired to use oleum with e.g. 5-10% sulphur trioxide as catalyst, a primary alcohol such as methanol must be used to prevent sulphonation.
- a diluent e.g. a primary alcohol such as methanol
- the decomposing action of sulphuric acid can be reduced by lowering the reaction temperature.
- the reaction can be carried out at temperatures ranging from about -30 C. to +50- 0., the preferred temperature range being -10 C. to +15 C.
- the compounds of Formula I are suitable for use as protective agents against the action of visible light and ultra-violet radiation for organic materials sensitive to this action.
- the starting compounds of Formula II employed in this process are also protective agents against light, but their value as such is greatly enhanced by the process as the compounds alkylated in the benzene nucleus provide far more efiective protection against light and radiation. For instance, it has been found that 2-ethyl-5'- tert.butyl-2'-ethoxy-N,N'-diphenyloxamide protects polyvinyl chloride and polypropylene more effectively from ultra-violet radiation than 2-ethyl-2'-ethoxy-N,N-diphenyloxamide.
- Another advantage of the compounds of Formula I is that they are more highly soluble in some of the organic materials that require protection of this nature, for instance polyalkylenes, and once fixed in the material are more resistant to migration than the new oxamides used as starting compounds in the process.
- the present invention relates further to the use of the oxamides of Formula I as ultra-violet absorbers.
- the oxamides of Formula I are either incorporated in the materials for protection or applied to the surface of the material to form a protective film. By absorbing the detrimental ultraviolet rays they safeguard light-sensitive materials from degradation.
- the oxamides produced by the present process can also be incorporated in suntan creams and lotions to absorb the ultra-violet radiation which causes erythema. But the suitable applications in plastics technology are far more numerous than in cosmetics and medicine.
- These oxamides can be used as protective additives in or on cellulose acetate, cellulose acetatebutyrate, polyethylene, polypropylene, polyvinyl chloride, polyvinyl chloride acetate, polyamides, polystyrene, ethyl cellulose, cellulose nitrate, polyvinyl alcohol, silicon rubber, cellulose propionate, melamine-formaldehyde resins, urea-formaldehyde resins, allyl casting resins, polymethyl methacrylate, polyesters and polyacrylonitrile.
- the material to be protected may be present in the form of film, sheet, rod, strip or panels, powders, granules, fibres or other solid forms, or as solutions, emulsions or dispersions.
- the disclosed protective agents are incorporated in or applied to the materials by the known methods.
- One important method of application consists in mixing the oxamide of Formula I with the polymer, e.g. polypropylene granules, in a kneader or other suitable machine, with subsequent extrusion. In this way homogeneous mixing is achieved, which is important for satisfactory protection.
- the moulding material containing the agent can be extruded in various forms, such as film, tubing or filament which may be woven into textile fabric.
- the UV-absorber is incorporated in the polymer before it is converted into textiles.
- formed textiles and fabrics can be treated with the compounds of Formula I, which in this case are applied from superfine dispersion in an aqueous or other suitable medium.
- This method is suitable for textiles of polyester and 4 cellulose acetate fibres.
- the compounds of Formula I need not necessarily be added to the final polymers. They can if desired be incorporated in the monomers or prepolymers prior to the reaction giving the final polymer.
- the oxamides produced by the disclosed process are suitable for stabilizing opaque, semi-opaque and translucent materials with a surface which is subject to degradation by ultra-violet radiation.
- examples are foamed plastics, opaque films and coatings, opaque papers, transparent and opaque colored plastics, fiuorescing pigments, automobile and furniture polishes, creams, lotions and the like, whether opaque, clear or translucent.
- the compounds of Formula I can be employed in combination with other UV-absorbers or with stabilizers. These mixtures of active substances often have a synergic action and protect the treated materials simultaneously against ultra-violet radiation, heat and oxidative degradation.
- the present invention relates further to the materials which contain one of the new compounds of Formula I for protection against ultra-violet radiation.
- the oxamides can be incorporated in the materials at any stage of processing using the known methods; the amounts used may vary within wide limits, e.g. from 0.01 to 5%, preferably 0.05 to 1%, relative to the weight of the material to be protected.
- M.P. stands for the melting point, parts and percentages are by weight and the temperatures are in degrees centigrade.
- Example 1 1000 parts of 100% sulphuric acid are run into 170 parts of methanol with vigorous stirring and cooling to -5 to- 0. Then 312 parts of 2-ethyl-2'-ethoxy-N,N'- diphenyloxamide are slowly added at 10 to -5, followed slowly at the same temperature by parts of tertiary butanol. The temperature is increased to +5 and the mixture reacted at this temperature for 6 hours with stirring. Subsequently it is extracted three times using 500 parts of chloro-benzene each time. The combined extracts are washed with 10% sodium carbonate solution, the chlorobenzene removed by steam distillation, and the distillation residue filtered and dried.
- a practically white crystalline mass is obtained in a yield of about 360 parts. It is readily pulverizable and its melting range is 107-l26. Its composition and constitution, as determined by gas chromatography, infra-red and nuclear resonance spectroscopy, is follows: approximately 80% Z-ethyl-5'-tert.butyl-2'-ethoxy-N,N-diphenyloxamide and approximately 20% 2-ethyl-4,5'-(di-tert.butyl)-2'-ethoxy- N,N'-diphenyloxarnide, with a very small amount of the starting oxamide.
- the amount of 100% sulphuric acid can be increased to 1200 parts and that of tertiary butanol to parts, on which a product is formed containing 60-70% 2-ethyl-4,5-di-(tert.butyl) 2 ethoxy-N,N'- diphenyloxamide, which crystallizes from cyclohexane and in the pure form melts at 91-92.
- the alkylated products obtained are more highly soluble at 20 in benzine of boiling point 100-120 than the starting compound:
- Example 2 The procedure is as in Example 1, except that 70 parts of iso-butylene are added to the solution of the starting compound in methanol-sulphuric acid in place of tertiary butanol. A product is obtained which has virtually the same composition as that of Example 1.
- Example 3 In place of tertiary butanol, the procedure of Example 1 is carried out with 150 parts of di-iso-butylene, the final product being obtained as a soft crystalline mass. It consists of approximately 70% 2-ethyl-5'-tert.octy1-2' ethoxy-N,N'-diphenyloxamide and about 30% 2-ethyl- 4,5'-di-(tert.octyl) 2 ethoxy-N,N'-diphenyl-oxamide.
- Example 4 From the isomeric compound 4-methyl-2-ethoxy- N,N-diphenyloxamide, 4-methyl-5'-tert.butyl-2-ethoxy- N,N'-diphenyloxamide, melting point 148149, is obtained in the same manner as in Example 4.
- Example 6 At -10 to 5' 750 parts of 100% sulphuric acid are added slowly with good stirring and cooling to a mixture of 145 parts of 2-ethoxy-N,N'-diphenyloxamide, 150 parts of tertiary butanol and 100 parts of methanol. Stirring is continued for 6 hours at 5 to 0. The reaction mixture is discharged onto ice and the precipitated crude product filtered and washed with water. Its melting range is 93-113".
- composition determined by gas chromatography, infra-red and nuclear resonance spectroscopy is about 65% 5-tertvbutyl-2-ethoxy-N,N-diphenyloxamide and about 35% 5,4'-di-(tert.butyl)-2- ethoxy-N,N'-diphenyloxamide. These two compounds melt at 1l71l8 and 136-137 respectively.
- Example 7 The reaction is carried out as in Example 1 using 2- ethyl-2'-(n-octyloxy) N,N' diphenyloxamide in place of 2-ethyl-2'-ethoxy N,N' diphenyloxamide. It gives 2-ethyl-5-tert.butyl-2-(n-octyloxy N,N' diphenyloxamide, melting point 70-71.
- Example 8 In a reaction vessel 30 parts of methanol are stirred, then 10 parts of ammonium sulphate are added. After cooling to 5 to 0 210 parts of 100% sulphuric acid are added at this temperature, followed by 57 parts of 2,4-dimethyl-2'-hydroxy-N,N-diphenyloxamide. In the next hour 40 parts of tertiary butanol are gradually added at 5 to 10. The reaction mixture is stirred further for 8 hours at 0-5". It is unloaded onto ice, giving a precipitate which is filtered, washed with sodium carbonate solution and water until free of sulphate ions, vacuum dried, and ground.
- Example 9 The procedure of Example 8 is followed, with the addition of 32 parts of iso-butylene in place of tertiary butanol. The same final product is obtained.
- Example 12 2 hydroxy-N,N'-diphenyloxamide 5,4'-di-tert.butyl)- 2-hydroxydiphenyloxamide, M.P. 162-164".
- Example 13 2,5 dimethyl-2'-hydroxy-N,N'-diphenyloxamide 2,5- dimethyl-3,5'-dj-(tert.butyl)-2'-hydroxy-N,N' diphenyloxamide, M.P. 173-174".
- Example 14 2 hydroxy-3'-ethylmercapto-N,N'-diphenyloxamide 3,5-di-(tert.butyl)-2-hydroxy 3' ethylmercapto-N,N'- diphenyloxamide, M.P. 176-180.
- Example 15 Di-iso-butylene2-ethyl-5'-tert.-octyl 2' hydroxy- N,N'-diphenyloxamide, M.P. 104-106.
- Example 18 Tetrapropylene 2-ethyl-5-tert.dodecyl 2' hydroxy- N,N'-diphenyloxamide, a colorless viscous oil.
- Example 19 the reaction is carried out as in Example 1 or 2 using 2-ethyl-2'-ethoxy- N,N-diphenyloxamide and the stated alcohol or olefin.
- Example 19 Iso-propanol 2-ethyl 2 ethoxy 4,3',5-tri-isopropyl- N,N-diphenyloxamide, a liquid mixture of isomers.
- Example 21 Heptene- 2 ethyl 2' ethoxy-S-tert.heptyl-N,N-diphenyloxamide, M.P. 7578.
- Example 4 In the following Examples 23 to 29 the procedure of Example 4 is employed with tertiary butanol.
- Example 23 2 ethoxy 4 tert.butyl-N,N'-diphenyloxamidw2- ethoxy-5,4'-di-(tert.butyl)-N,N' diphenyloxamide, M.P. 136-137
- Example 24 Z-methoxy 2' rnethyl-N,N'-diphenyloxamidea 2-methoxy-S-tert.butyl-2'-methyl-N,N-diphenyloxamide, M.P. 144-145
- Example 25 2-methoxy 4' methyl-N,N'-diphenyloxarnide 2-methoxy-5-tert.butyl-4'-methyl-N,N'-diphenyloxamide, M.P. l77-l79.
- Example 28 Z-n-butoxy 2 ethyl-N,N'-diphenyloxamide- 2-n-butoxy 5 tert.buty1-2'-ethyl-N,N'-diphenyloxamide, M.P. 69-71.
- Example B Comparative tests with rigid polyvinyl chloride in place of polypropylene are carried out as in Example A. The samples show embrittlement after 800, 2000 and 4000 hours respectively.
- Example C Polypropylene containing homogeneously distributed therein 0.5 of the compound produced as in Example 7 is tested as given in Example A. It withstands exposure to xenon light for 3000 hours without becoming brittle.
- Example D The mixture of monobutylated and dibutylated oxamide produced as in Example 1 is incorporated in polyamide 6 in an amount of 0.3%.
- a control sample of the material without the additive turns yellow and brittle after 3000 hours, whereas the sample containing the oxamide mixture withstands 8000 hours exposure without change.
- Example E 0.5% of the compound named in Example 16 is incorporated in unstabilized polypropylene. Exposure tests alongside polypropylene without the additive show that 5 it is much more resistant to the action of light and ultraviolet radiation. In tests for heat stability at 140 the first sample does not become brittle until after 14 days, whereas the unprotected sample is brittle after only one days exposure.
- Example F In a high pressure polyethylene (Lupolen 1810 H, registered trademark) 0.5% of the final product of Example 21 is incorporated by the normal method. Sheets of 0.3 mm. thickness are moulded with this material, With the same polyethylene containing 0.5% of the starting compound 2-ethyl-2'ethoxy-N,N'-diphenyloxamide, and with polyethylene containing no additive. The sheets are exposed in the Xenotest 450 apparatus until brittleness appears. The times that elapse before this effect appears are about 800 hours for the sample without additive, about 1500 hours for the one containing 0.5 of the starting compound, and about 3500 hours for the sample protected with 0.5 of the product of Example 21.
- a high pressure polyethylene Lipolen 1810 H, registered trademark
- Example 1 C H (tert.) NH OO CO NH C2115 2 :5 (III)
- rings A and B are selected from the group consisting of hydroxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 8 carbon atoms, and alkylmercapto of l to 8 carbon atoms.
- a process according to claim 1 which comprises alkylating a compound of Formula II wherein one or both of the rings A; and B are unsubstituted or substituted by one or more members of the group consisting of hydroxyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 8 carbon atoms, and alkylmercapto of 1 to 8 carbon atoms, with 1 to 4 moles, per mole of Compound H, of an alkylating agent containing 3 to 9 carbon atoms and selected from the group consisting of olefins, secondary alcohols, and tertiary alcohols, at a temperature of 30 to +50 C.
- sulphuric acid of a concentration greater than 90% and a reaction dampening agent selected from the group consisting of formamide, dimethyl formamide, ammonium sulfate, the sulfates of alkylamines, and the sulfates of primary alcohols.
- a reaction dampening agent selected from the group consisting of formamide, dimethyl formamide, ammonium sulfate, the sulfates of alkylamines, and the sulfates of primary alcohols.
- alkylating agent is selected from the group consisting of propene, l-butene, Z-butene, iso-butylene, 2-methyl-lbutene, 2-methyl-2-butene, B-methyl-l-butene, l-pentene,
- a process according to claim 1 wherein the concentration of sulphuric acid is at least 8.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
THIS INVENTION RELATES TO A PROESS FOR THE PRODUCTION OF THE ALKYLATED N, N'' -DIPHENYLOXANIDES OF FORMULA
(PHENYL-NH-CO-CO-NH-)BENZENE
IN WHICH 1 TO 4 SECONDARY OR TERTIARY ALKYL RADICALS HAVING 3 TO 20 CARBON ATOMS ARE BOUND TO THE NUCLEI A AND/ OR B AND THE NUCLEI A AND B MAY ADDITIONALLY CONTAIN HYDROXYL GROUPS AND/OR HYDROCARBON RADICALS HAVING 1 TO 20 CARBON ATOMS WHICH MAY BE BOUND THROUGH OXYGEN OR SULPH8UR ATOMS. THESE COMPOUNDS ABSORB ULTRAVIOLET RAYS AND PROTECT LIGHT-SENSITIVE ORGANIC MATERIALS, NOBLY PLASTICS, FROM THE DETERMINTAL ACTION OF THIS RADIATION.
(PHENYL-NH-CO-CO-NH-)BENZENE
IN WHICH 1 TO 4 SECONDARY OR TERTIARY ALKYL RADICALS HAVING 3 TO 20 CARBON ATOMS ARE BOUND TO THE NUCLEI A AND/ OR B AND THE NUCLEI A AND B MAY ADDITIONALLY CONTAIN HYDROXYL GROUPS AND/OR HYDROCARBON RADICALS HAVING 1 TO 20 CARBON ATOMS WHICH MAY BE BOUND THROUGH OXYGEN OR SULPH8UR ATOMS. THESE COMPOUNDS ABSORB ULTRAVIOLET RAYS AND PROTECT LIGHT-SENSITIVE ORGANIC MATERIALS, NOBLY PLASTICS, FROM THE DETERMINTAL ACTION OF THIS RADIATION.
Description
United States Patent Oflice 3,808,273 Patented Apr. 30, 1974 3,808,273 PROCESS FOR THE PRODUCTION OF ALKYLATED N ,N'-DIPHENYLOXAMIDES Evelyne Burdet, Mulhouse, France, and Kurt Hofer,
Munchenstein, Basel-Land, Rudolf Moesch, Stein,
Aargau, and Alfred Schilli, Reinach, Basel-Land, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland No Drawing. Filed Aug. 10, 1971, Ser. No. 170,660
Int. Cl. C07c 103/26 US. Cl. 260-559 S 11 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a process for the production of the alkylated N,N'-diphenyloxamides of formula @NH-C o-c -NH- A in which 1 to 4 secondary or tertiary alkyl radicals having 3 to 20 carbon atoms are bound to the nuclei A and/ or B and the nuclei A and B may additionally contain hydroxyl groups and/or hydrocarbon radicals having 1 to 20 carbon atoms which may be bound through oxygen or sulphur atoms. These compounds absorb ultraviolet rays and protect light-sensitive organic materials, notably plastics, from the detrimental action of this radiation.
This invention relates to a process for the production of alkylated N,N'-diphenyloxamides of the formula in which 1 to 4 secondary or tertiary alkyl radicals having 3 to 20 carbon atoms are bound to the nuclei A and/or B and the nuclei A and B may additionally contain hydroxyl groups and/or hydrocarbon radicals having 1 to 20 carbon atoms which may be bound through oxygen or sulphur atoms. This new process is characterized by the alkylation, in the presence of sulphuric acid, of 1 mol of a compound of the formula in which the nuclei A and/or B may contain hydroxyl groups and/or hydrocarbon radicals having 1 to 20 carbon atoms which may be bound through oxygen or sulphur atoms, with 1 to 4 mols of an olefin having 3 to 20 carbon atoms, or a secondary or tertiary alcohol. Employing this reaction, N,N-diphenyloxamides alkylated in the nucleus are obtained in very good yield. This is surprising since in the analogous reaction of other N-phenylamides, for example N-phenylacetamide, no or very little nucleoalkylated amide is obtained. The dilference is probably due to the fact that the amides of Formula II, in contrast to other amides such as N-phenylacetamide, are stable under the reaction conditions.
A considerable number of starting compounds of the General Formula II are known. New members of the series can be easily synthesized by generally known methods. Each of the nuclei A and B in the General Formula II may be unsubstituted or substituted. The following substituents are suitable: the hydroxyl group, which preferably occurs only once in a benzene nucleus, straight or branched alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. butyl, iso-amyl, octyl, nonyl, dodecyl and octadecyl, cycloalkyl radicals such as the cyclohexyl radical, aryl radicals, in particular phenyl, aralkyl radicals such as the benzyl radical, alkoxy radicals such as methoxy, ethoxy, iso-propoxy, n-butoxy, nhexoxy, n-octoxy, dodecyloxy and octadecyloxy, alkylmercapto radicals such as methylmercapto, ethylmercapto,
butylmercapto, hexylmercapto and octylmercapto, aryloxy radicals such as phenoxy, and arylmercapto such as phenylmercapto.
The preferred substitutents on the nuclei A and B of the starting compounds of Formula II are hydroxyl groups, alkyl groups having 1 to 4 carbon atoms and alkoxy and alkylmercapto groups having 1 to 8 carbon atoms.
The alkylating agent may be chosen from the following: propene, l-butene, Z-butene, iso-butylene, 2-methyll-butene, 2-methyl-2-butene, 3-methyl-l-butene, l-pentene, Z-ethyl-l-butene, 3,3-dimethyl-l-butene, l-hexene, 3- methyl-l-pentene, 4 methyl-2-pentene, 2,4-dirnethyl-2- pentene, 4,4-dimethyl 1 pentene, 2-heptene, 3-methyll-hexene, tripropylene, tetrapropylene, di-iso-butylene, triiso-butylene, l-hexadecene, l-heptadecene, l-octadecene, l-eicosene, iso-propanol, secondary butanol, tertiary butanol, 2-methyl-2-butanol, Z-pentanol, 3-pentanol, 2,3-dimethyl-Z-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,4-dimethyl-2-pentanol, 3-heptanol, 2-rnethyl-2-hexanol, 3-methyl-3-hexanol, S-methyl- S-hexanol, 3-ethyl-4-hexanol, 2,2-dimethyl-3-hexanol, 3, 4-dimethyl-3-hexanol, 2 methyl-Z-heptanol, 6-methyl-2- heptanol, 4-octanol, 2,3,4-trimethyl-3-pentanol, 2-methyl- 2-octanol, 3-methyl-4-octanol, 5-nonanol, 3,6-dimethyl-3- octanol, 4-methyl-4-nonanol, 2,6,8 trimethyl-4-nonanol, 2-nonadecanol.
The olefins and the secondary or tertiary alcohols containing 3 to 12 or more, especially 3 to 9, carbon atomsare given preference as alkylating agents so that the final products of Formula I bear preferably 1 to 4 secondary or tertiary alkyl radicals having 3 to 12 or in particular 3 to 9 carbon atoms.
In the present process sulphuric acid is used both as catalyst and as condensing agent. In order to be sufficiently effective it must be employed in highly concentrated form, i.e. of more than preferably -100% strength. Very low percentage oleum containing e.g. up to 5% sulphur trioxide, is also suitable. In order to prevent the decomposing action of the sulphuric acid on the 0xamides to the greatest possible extent, it is advisable to dampen the activity of the acid by adding a diluent such as formamide, dimethyl formamide, ammonium sulphate, or one of the sulphates of alkylamines or primary alcohols. A highly suitable diluent or damping agent of this type is methanol, which is converted into methylsulphuric acid by sulphuric acid. When secondary or tertiary alcohols are employed as alkylating agents, water is split off in the reaction; it is therefore advisable to slowly add additional sulphuric acid in the course of the reaction so that the freed water does not dilute the sulphuric acid too heavily. It is best to choose the amount and the concentration of sulphuric acid so that its total water content at the end of the reaction (from the methanol present, when used, and/or from the alcohol used for alkylating) does not exceed 15%. If oleum is used, it is advisable to set the reaction mixture with a diluent, e.g. a primary alcohol such as methanol, in a quantity sufficient to preclude sulphonation of the diphenyl oxamide. If it is desired to use oleum with e.g. 5-10% sulphur trioxide as catalyst, a primary alcohol such as methanol must be used to prevent sulphonation.
The decomposing action of sulphuric acid can be reduced by lowering the reaction temperature. The reaction can be carried out at temperatures ranging from about -30 C. to +50- 0., the preferred temperature range being -10 C. to +15 C.
If Friedel-Crafts catalysts such as borofiuoride etherate in place of sulphuric acid are employed for the reaction, the yields are substantially lower and the products of greatly inferior purity. Good results are obtained when, jointly with sulphuric acid, a second catalyst is employed,
such as phosphoric acid, polyphosphoric acid, aluminium chloride, borofluoride, hydrogen fluoride or zinc chloride. However, the results obtained with sulphuric acid as sole catalyst are so good that the joint use of other, substantially dearer catalysts does not normally offer any advantages.
The compounds obtained by the new process described herein are accessible by way of a known process. In this process aniline or aniline derivatives are reacted with compounds yielding the oxalyl radical. The intermediates required for this route of synthesis are often difficult to obtain and expensive. In comparison, the present process provides a far more favorable route to compounds of Formula I.
The compounds of Formula I are suitable for use as protective agents against the action of visible light and ultra-violet radiation for organic materials sensitive to this action. The starting compounds of Formula II employed in this process are also protective agents against light, but their value as such is greatly enhanced by the process as the compounds alkylated in the benzene nucleus provide far more efiective protection against light and radiation. For instance, it has been found that 2-ethyl-5'- tert.butyl-2'-ethoxy-N,N'-diphenyloxamide protects polyvinyl chloride and polypropylene more effectively from ultra-violet radiation than 2-ethyl-2'-ethoxy-N,N-diphenyloxamide. Another advantage of the compounds of Formula I is that they are more highly soluble in some of the organic materials that require protection of this nature, for instance polyalkylenes, and once fixed in the material are more resistant to migration than the new oxamides used as starting compounds in the process.
The present invention relates further to the use of the oxamides of Formula I as ultra-violet absorbers. For this purpose they are either incorporated in the materials for protection or applied to the surface of the material to form a protective film. By absorbing the detrimental ultraviolet rays they safeguard light-sensitive materials from degradation.
The oxamides produced by the present process can also be incorporated in suntan creams and lotions to absorb the ultra-violet radiation which causes erythema. But the suitable applications in plastics technology are far more numerous than in cosmetics and medicine. These oxamides can be used as protective additives in or on cellulose acetate, cellulose acetatebutyrate, polyethylene, polypropylene, polyvinyl chloride, polyvinyl chloride acetate, polyamides, polystyrene, ethyl cellulose, cellulose nitrate, polyvinyl alcohol, silicon rubber, cellulose propionate, melamine-formaldehyde resins, urea-formaldehyde resins, allyl casting resins, polymethyl methacrylate, polyesters and polyacrylonitrile. They can also be used to protect natural products such as rubber, cellulose, wool and silk. The material to be protected may be present in the form of film, sheet, rod, strip or panels, powders, granules, fibres or other solid forms, or as solutions, emulsions or dispersions.
The disclosed protective agents are incorporated in or applied to the materials by the known methods. One important method of application consists in mixing the oxamide of Formula I with the polymer, e.g. polypropylene granules, in a kneader or other suitable machine, with subsequent extrusion. In this way homogeneous mixing is achieved, which is important for satisfactory protection. The moulding material containing the agent can be extruded in various forms, such as film, tubing or filament which may be woven into textile fabric. In this method of application the UV-absorber is incorporated in the polymer before it is converted into textiles. Alternatively, formed textiles and fabrics can be treated with the compounds of Formula I, which in this case are applied from superfine dispersion in an aqueous or other suitable medium. This method is suitable for textiles of polyester and 4 cellulose acetate fibres. The compounds of Formula I need not necessarily be added to the final polymers. They can if desired be incorporated in the monomers or prepolymers prior to the reaction giving the final polymer.
Besides clear films and the other aforenamed products, the oxamides produced by the disclosed process are suitable for stabilizing opaque, semi-opaque and translucent materials with a surface which is subject to degradation by ultra-violet radiation. Examples are foamed plastics, opaque films and coatings, opaque papers, transparent and opaque colored plastics, fiuorescing pigments, automobile and furniture polishes, creams, lotions and the like, whether opaque, clear or translucent.
The compounds of Formula I can be employed in combination with other UV-absorbers or with stabilizers. These mixtures of active substances often have a synergic action and protect the treated materials simultaneously against ultra-violet radiation, heat and oxidative degradation.
In order to obtain protection against ultra-violet radiation it is essential to incorporate the new compounds in the material or to coat the material with them. Lightsensitive foods such as fruit, cooking fats and butter can be protected by storage in plastic film or sheet containing a compound of Formula I.
The present invention relates further to the materials which contain one of the new compounds of Formula I for protection against ultra-violet radiation. As stated in the foregoing, the oxamides can be incorporated in the materials at any stage of processing using the known methods; the amounts used may vary within wide limits, e.g. from 0.01 to 5%, preferably 0.05 to 1%, relative to the weight of the material to be protected.
In the following examples M.P. stands for the melting point, parts and percentages are by weight and the temperatures are in degrees centigrade.
EXAMPLES OF THE PROCESS OF PRODUCTION Example 1 1000 parts of 100% sulphuric acid are run into 170 parts of methanol with vigorous stirring and cooling to -5 to- 0. Then 312 parts of 2-ethyl-2'-ethoxy-N,N'- diphenyloxamide are slowly added at 10 to -5, followed slowly at the same temperature by parts of tertiary butanol. The temperature is increased to +5 and the mixture reacted at this temperature for 6 hours with stirring. Subsequently it is extracted three times using 500 parts of chloro-benzene each time. The combined extracts are washed with 10% sodium carbonate solution, the chlorobenzene removed by steam distillation, and the distillation residue filtered and dried. A practically white crystalline mass is obtained in a yield of about 360 parts. It is readily pulverizable and its melting range is 107-l26. Its composition and constitution, as determined by gas chromatography, infra-red and nuclear resonance spectroscopy, is follows: approximately 80% Z-ethyl-5'-tert.butyl-2'-ethoxy-N,N-diphenyloxamide and approximately 20% 2-ethyl-4,5'-(di-tert.butyl)-2'-ethoxy- N,N'-diphenyloxarnide, with a very small amount of the starting oxamide.
If sulphuric acid of about 97% instead of 100% strength is used and 60 parts of tertiary butanol in place of 90, an approximately 93-95% monobutylation product is obtained, from which can be obtained by re-crystallization, e.g. from iso-propanol, the pure 2-ethyl-5'-tert.- butyl-2-ethoxy-N,N'-diphenyloxamide, which melts at 136-138.
Alternatively, the amount of 100% sulphuric acid can be increased to 1200 parts and that of tertiary butanol to parts, on which a product is formed containing 60-70% 2-ethyl-4,5-di-(tert.butyl) 2 ethoxy-N,N'- diphenyloxamide, which crystallizes from cyclohexane and in the pure form melts at 91-92.
The alkylated products obtained are more highly soluble at 20 in benzine of boiling point 100-120 than the starting compound:
Solubility at 20 N,N-diphenyloxamide Mg./l. Percent A 2-ethyl-2-ethoxy-(starting compound) 5, 000 0.5 B 2ethyl-2-ethoxy-5-tert.butyl 12, 000 1. 2 O 2-ethyl-2-ethoxy-4,5-di-(tert.butyl) 100, 000 10 15, 000 1. 5
Example 2 The procedure is as in Example 1, except that 70 parts of iso-butylene are added to the solution of the starting compound in methanol-sulphuric acid in place of tertiary butanol. A product is obtained which has virtually the same composition as that of Example 1.
Example 3 In place of tertiary butanol, the procedure of Example 1 is carried out with 150 parts of di-iso-butylene, the final product being obtained as a soft crystalline mass. It consists of approximately 70% 2-ethyl-5'-tert.octy1-2' ethoxy-N,N'-diphenyloxamide and about 30% 2-ethyl- 4,5'-di-(tert.octyl) 2 ethoxy-N,N'-diphenyl-oxamide.
Example 4 Example 5 From the isomeric compound 4-methyl-2-ethoxy- N,N-diphenyloxamide, 4-methyl-5'-tert.butyl-2-ethoxy- N,N'-diphenyloxamide, melting point 148149, is obtained in the same manner as in Example 4.
Example 6 At -10 to 5' 750 parts of 100% sulphuric acid are added slowly with good stirring and cooling to a mixture of 145 parts of 2-ethoxy-N,N'-diphenyloxamide, 150 parts of tertiary butanol and 100 parts of methanol. Stirring is continued for 6 hours at 5 to 0. The reaction mixture is discharged onto ice and the precipitated crude product filtered and washed with water. Its melting range is 93-113". Its composition determined by gas chromatography, infra-red and nuclear resonance spectroscopy is about 65% 5-tertvbutyl-2-ethoxy-N,N-diphenyloxamide and about 35% 5,4'-di-(tert.butyl)-2- ethoxy-N,N'-diphenyloxamide. These two compounds melt at 1l71l8 and 136-137 respectively.
Example 7 The reaction is carried out as in Example 1 using 2- ethyl-2'-(n-octyloxy) N,N' diphenyloxamide in place of 2-ethyl-2'-ethoxy N,N' diphenyloxamide. It gives 2-ethyl-5-tert.butyl-2-(n-octyloxy N,N' diphenyloxamide, melting point 70-71.
Example 8 In a reaction vessel 30 parts of methanol are stirred, then 10 parts of ammonium sulphate are added. After cooling to 5 to 0 210 parts of 100% sulphuric acid are added at this temperature, followed by 57 parts of 2,4-dimethyl-2'-hydroxy-N,N-diphenyloxamide. In the next hour 40 parts of tertiary butanol are gradually added at 5 to 10. The reaction mixture is stirred further for 8 hours at 0-5". It is unloaded onto ice, giving a precipitate which is filtered, washed with sodium carbonate solution and water until free of sulphate ions, vacuum dried, and ground. 75 parts of crude 2,4-dimethyl- 3,5-di-(tert.butyl) 2' hydroxy-N,N'-diphenyloxamide in the form of a colorless powder are obtained, which after re-crystallization from iso-propanol melts at 152- 155".
Example 9 The procedure of Example 8 is followed, with the addition of 32 parts of iso-butylene in place of tertiary butanol. The same final product is obtained.
In the following Examples 10 to 15 the given starting compounds are reacted with tertiary butanol or iso-butylene as in Examples 8 and 9 to yield the named products which are distinguished by their melting points.
Example 10 2-ethyl 2' hydroxy-N,N'-diphenyloxamide 2-ethyl- 5'-tert.buty1-2'-hydroxy-N,N'-diphenyloxamide, M.P. 163
Example 11 2-ethyl 2' hydroxy-N,N'-diphenyloxamide 2-ethyl- 3,5'-di-(tert.butyl) 2 hydroxy-N,N'-diphenyloxamide, M.P. 103-106".
Example 12 2 hydroxy-N,N'-diphenyloxamide 5,4'-di-tert.butyl)- 2-hydroxydiphenyloxamide, M.P. 162-164".
Example 13 2,5 dimethyl-2'-hydroxy-N,N'-diphenyloxamide 2,5- dimethyl-3,5'-dj-(tert.butyl)-2'-hydroxy-N,N' diphenyloxamide, M.P. 173-174".
Example 14 2 hydroxy-3'-ethylmercapto-N,N'-diphenyloxamide 3,5-di-(tert.butyl)-2-hydroxy 3' ethylmercapto-N,N'- diphenyloxamide, M.P. 176-180.
Example 15 Example 16 Di-iso-butylene2-ethyl-5'-tert.-octyl 2' hydroxy- N,N'-diphenyloxamide, M.P. 104-106.
Example 17 Tripropylene2-ethyl-5-tert.nonyl-2-hydroxy N,N'- diphenyloxamide, M.P. 80-82.
Example 18 Tetrapropylene 2-ethyl-5-tert.dodecyl 2' hydroxy- N,N'-diphenyloxamide, a colorless viscous oil.
In the following Examples 19 to 22 the reaction is carried out as in Example 1 or 2 using 2-ethyl-2'-ethoxy- N,N-diphenyloxamide and the stated alcohol or olefin.
Example 19 Iso-propanol 2-ethyl 2 ethoxy 4,3',5-tri-isopropyl- N,N-diphenyloxamide, a liquid mixture of isomers.
Example 20 Tertiary amyl alcohol-a2-ethyl-2'-ethoxy-5'-tert.amyl- N,N'-diphenyloxamide, M.P. 98-100".
Example 21 Heptene- 2 ethyl 2' ethoxy-S-tert.heptyl-N,N-diphenyloxamide, M.P. 7578.
Example 22 Tripropylene- 2-ethyl 2 ethoxy-'-isononyl- N,N'- diphenyloxamide, M.P. 8487.
In the following Examples 23 to 29 the procedure of Example 4 is employed with tertiary butanol.
Example 23 2 ethoxy 4 tert.butyl-N,N'-diphenyloxamidw2- ethoxy-5,4'-di-(tert.butyl)-N,N' diphenyloxamide, M.P. 136-137 Example 24 Z-methoxy 2' rnethyl-N,N'-diphenyloxamidea 2-methoxy-S-tert.butyl-2'-methyl-N,N-diphenyloxamide, M.P. 144-145 Example 25 2-methoxy 4' methyl-N,N'-diphenyloxarnide 2-methoxy-5-tert.butyl-4'-methyl-N,N'-diphenyloxamide, M.P. l77-l79.
Example 26 2-n-octyloxy 2 methy1-N,N'-diphenyloxamide 2-noctyloxy 5 tert.butyl-2'-methyl-N,N'-diphenyloxamide, M.P. 8385.
Example 27 2-n-octyloxy 4' methyl-N,N'-diphenyloxamide 2-noctyloxy 5 tert.butyl-4'-methyl-N,N-diphenyloxamide, M.P. 96-98".
Example 28 Z-n-butoxy 2 ethyl-N,N'-diphenyloxamide- 2-n-butoxy 5 tert.buty1-2'-ethyl-N,N'-diphenyloxamide, M.P. 69-71.
Example 29 2-methoxy-4'-n-octylthio N,N' diphenyloxamide- 2- methoxy-5-tert.butyl 4' n octylthio-N,N'-diphenyloxamide, M.P. 75-80.
EXAMPLES OF APPLICATION Example A Three samples of polypropylene, the first without a protective additive, the second containing 0.5% of the compound 2-ethyl-2-ethoxy-N,N'-diphenyloxamide and the third 0.5 of Z-ethyl-5'-tert.butyl-2-ethoxy-N,N-diphenyloxamide, are exposed to light in the Xenotest 450" apparatus. The time is determined at which the samples turn brittle, which is 300, 1500 and 2500 hours respectively. These findings show that although the oxamide used as starting compound in Example 1 is quite a good protective agent against light and ultraviolet radiation, alkylation in the benzene nucleus in accordance with the present invention transforms it into a far more effective compound.
Example B Comparative tests with rigid polyvinyl chloride in place of polypropylene are carried out as in Example A. The samples show embrittlement after 800, 2000 and 4000 hours respectively.
Example C Polypropylene containing homogeneously distributed therein 0.5 of the compound produced as in Example 7 is tested as given in Example A. It withstands exposure to xenon light for 3000 hours without becoming brittle.
Example D The mixture of monobutylated and dibutylated oxamide produced as in Example 1 is incorporated in polyamide 6 in an amount of 0.3%. In exposure tests in the Xenotest 450 apparatus a control sample of the material without the additive turns yellow and brittle after 3000 hours, whereas the sample containing the oxamide mixture withstands 8000 hours exposure without change.
8 Example E 0.5% of the compound named in Example 16 is incorporated in unstabilized polypropylene. Exposure tests alongside polypropylene without the additive show that 5 it is much more resistant to the action of light and ultraviolet radiation. In tests for heat stability at 140 the first sample does not become brittle until after 14 days, whereas the unprotected sample is brittle after only one days exposure.
Example F In a high pressure polyethylene (Lupolen 1810 H, registered trademark) 0.5% of the final product of Example 21 is incorporated by the normal method. Sheets of 0.3 mm. thickness are moulded with this material, With the same polyethylene containing 0.5% of the starting compound 2-ethyl-2'ethoxy-N,N'-diphenyloxamide, and with polyethylene containing no additive. The sheets are exposed in the Xenotest 450 apparatus until brittleness appears. The times that elapse before this effect appears are about 800 hours for the sample without additive, about 1500 hours for the one containing 0.5 of the starting compound, and about 3500 hours for the sample protected with 0.5 of the product of Example 21.
Moreover, migration to the surface (blooming) of the starting compound is observable in the second sample, whereas this effect is absent in the one containing the product of Example 21.
Formulae of representative alkylated N,N-diphenyloxamides are as follows:
Example 1 C H (tert.) NH OO CO NH C2115 2 :5 (III) Example 7 4O C H (tert.)
@NHC o-o 0-NH 0 38 110 2115 (IV) Example 14 (IJ4Hq(tert.) @-NHC o-o o-NH@ S 02115 OH onzmtert.) v
Example 15 t hmoert.) (ll4H (tert.) NHO o-o O-NEhQ H H 4H (tert.)
C4H9(t6l't. (VI) Example 16 0811mm.
-NH-C o-o O--NH@ H zHa (VII) Having thus disclosed the invention what is claimed is: 1. A process for the production of an alkylated phenyloxamide of the formula wherein one or both or rings A and B is substituted by 1 to 4 secondary or tertiary alkyl radicals having 3 to 20 carbon atoms and further unsubstituted or substituted by hydroxy and/or hydrocarbon radicals containing 1 to carbon atoms bound directly or through an oxygen or sulphur atom to the ring, which process comprises alkyating a compound of the formula wherein one or both of rings A and B are unsubstituted or substituted by hydroxy and/or hydrocarbon radicals containing 1 to 20 carbon atoms bound directly or through an oxygen or sulphur atom to the ring, with 1 to 4 moles, per mole of Compound II, of an alkylating agent containing 3 to 20 carbon atoms and selected from the group consisting of olefins, secondary alcohols, and tertiary alcohols, in the presence of concentrated sulphuric acid and a reaction dampening agent selected from the group consisting of formamide, dimethyl formamide, ammonium sulfate, sulfates of alkylamines, and the sulfates of primary alcohols and at a temperature of 30 to +50 C.
2. A process according to claim 1 wherein the compound of Formula II contains no more than 1 hydroxy] group on each benzene nucleus.
3. A process according to claim 1 wherein the substituents on rings A and B are selected from the group consisting of hydroxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 8 carbon atoms, and alkylmercapto of l to 8 carbon atoms.
4. A process according to claim 1 wherein the alkylating agent contains 3 to 9 carbon atoms.
5. A process according to claim 1 which comprises alkylating a compound of Formula II wherein one or both of the rings A; and B are unsubstituted or substituted by one or more members of the group consisting of hydroxyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 8 carbon atoms, and alkylmercapto of 1 to 8 carbon atoms, with 1 to 4 moles, per mole of Compound H, of an alkylating agent containing 3 to 9 carbon atoms and selected from the group consisting of olefins, secondary alcohols, and tertiary alcohols, at a temperature of 30 to +50 C. and in the presence of sulphuric acid of a concentration greater than 90% and a reaction dampening agent selected from the group consisting of formamide, dimethyl formamide, ammonium sulfate, the sulfates of alkylamines, and the sulfates of primary alcohols.
6. A process according to claim 1 wherein the alkylating agent is selected from the group consisting of propene, l-butene, Z-butene, iso-butylene, 2-methyl-lbutene, 2-methyl-2-butene, B-methyl-l-butene, l-pentene,
2 ethyl 1 butene, 3,3-dimethyl-1-butene, l-hexene, 3- 50 10 methyl 1 pentene, 4-methyl-2-pentene, 2,4-dimethyl-2- pentene, 4,4-dimethyl-l-pentene, 2-heptene, 3-methyl-1- hexene, tripropylene, tetrapropylene, di-iso-butylene, triiso-butylene, l-hexadecene, l-heptadecene, l-octadecene, l-eicosene, iso-propanol, secondary butanol, tertiary butanol, 2-methyl-2-butanol, Z-pentanol, 3-pentanol, 2,3- dimethyl-Z-butanol, Z-methyl-Z-pentanol, 2 methyl 3- pentanol, 3-methyl-3-pentanol, 2,4-dimethyl-2-pentanol, 3 heptanol, 2 methyl-2-hexanol, 3-methyl-3-hexanol, 5- methyl-3-hexanol, 3 ethyl 4 hexanol, 2,2-dimethyl-3- hexanol, 3,4-dimethyl-3- hexanol, Z-methyl-Z-heptanol, 6- methyl Z-heptanol, 4-octanol, 2,3,4-trimethyl-3-pentanol, 2-methyl-2-octanol, 3-methyl-4-octanol, 5-nonanol, 3,6- dimethyl-3-octanol, 4-methyl-4-nonanol, 2,6,8-trimethyl- 4-nonanol, and Z-nonadecanol.
7. A process according to claim 1 wherein the concentration of sulphuric acid is at least 8. A process according to claim 1 wherein the sulphuric acid contains up to 5% sulphur trioxide.
9. A process according to claim 1 wherein there is also present during the alkylation a compound selected from the group consisting of phosphoric acid, polyphosphoric acid, aluminum chloride, borofluoride, hydrogen fluoride and zinc chloride.
10. A process according to claim 5 wherein 2-ethyl-2'- hydroxy-N,N'-diphenyloxamide is alkylated with di-isobutylene or tetrapropylene.
11. A process according to claim 5 wherein 2-ethyl- 2'(n-octyloxy)-N,N'diphenyloxamide or 2-methoxy-4'-noctylthio-N,N'-diphenyloxamide is alkylated with tertiary butanol.
References Cited UNITED STATES PATENTS Morrison et al.: Organic Chemistry, pp. 252-59, 287, 292 (Allyn & Bacon, Inc.i) Boston) (1959).
Yasue et al.: Chem. A stracts, vol. 52, col. 6227d-h (1958).
HARRY I. MOATZ, Primary Examiner US. Cl. X.R.
260-558 R; 558 S, 559 T, 45.9 R
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00170660A US3808273A (en) | 1971-08-10 | 1971-08-10 | Process for the production of alkylated n,n'-diphenyloxamides |
US405331A US3906041A (en) | 1968-02-19 | 1973-09-07 | Oxalic acid derivatives |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00170660A US3808273A (en) | 1971-08-10 | 1971-08-10 | Process for the production of alkylated n,n'-diphenyloxamides |
Publications (1)
Publication Number | Publication Date |
---|---|
US3808273A true US3808273A (en) | 1974-04-30 |
Family
ID=22620781
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00170660A Expired - Lifetime US3808273A (en) | 1968-02-19 | 1971-08-10 | Process for the production of alkylated n,n'-diphenyloxamides |
Country Status (1)
Country | Link |
---|---|
US (1) | US3808273A (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3904582A (en) * | 1974-07-30 | 1975-09-09 | Bell Telephone Labor Inc | Antioxidants for polyolefins |
US4003875A (en) * | 1966-02-07 | 1977-01-18 | Ciba-Geigy Corporation | Asymmetrical oxalic acid diaryl amide stabilizers |
US4412024A (en) * | 1981-09-14 | 1983-10-25 | Sandoz Ltd. | Concentrated solutions of aromatic oxamide stabilizers |
US4485034A (en) * | 1980-09-20 | 1984-11-27 | Sandoz Ltd. | Aromatic oxamides useful as stabilizers |
US4489186A (en) * | 1982-07-05 | 1984-12-18 | Mitsubishi Gas Chemical Company, Inc. | Polyphenylene ether resin composition |
US4572807A (en) * | 1981-03-21 | 1986-02-25 | Henkel Kommanditgesellschaft Auf Aktien | Oligophosphonic acids, oligophosphinic acids, and process of preparation |
US4652493A (en) * | 1979-05-25 | 1987-03-24 | Bayer Aktiengesellschaft | Self-curing material for the production of a weather-resistant, non-yellowing support bandage |
US4833038A (en) * | 1988-03-14 | 1989-05-23 | Ppg Industries, Inc. | UV curable coatings containing oxalanilide stabilizers, method of curing, and coated substrates therefrom |
US4920169A (en) * | 1986-12-02 | 1990-04-24 | Sandoz Ltd. | Oxalic acid di(phenylamides) and use thereof as UV absorbers |
US4921726A (en) * | 1988-03-14 | 1990-05-01 | Ppg Industries, Inc. | UV curable coatings containing oxalanilide stabilizers, method of curing, and coated substrates therefrom |
FR2735139A1 (en) * | 1995-06-07 | 1996-12-13 | Clariant Finance Bvi Ltd | COATING COMPOSITION COMPRISING A FILM-FORMING POLYMER AND A STABILIZING POLYMER COMPOSITION |
US5716667A (en) * | 1994-12-01 | 1998-02-10 | Kansai Paint Co., Ltd. | Method of temporarily protecting finished coating film on automobile body |
-
1971
- 1971-08-10 US US00170660A patent/US3808273A/en not_active Expired - Lifetime
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4003875A (en) * | 1966-02-07 | 1977-01-18 | Ciba-Geigy Corporation | Asymmetrical oxalic acid diaryl amide stabilizers |
US3904582A (en) * | 1974-07-30 | 1975-09-09 | Bell Telephone Labor Inc | Antioxidants for polyolefins |
US4652493A (en) * | 1979-05-25 | 1987-03-24 | Bayer Aktiengesellschaft | Self-curing material for the production of a weather-resistant, non-yellowing support bandage |
US4485034A (en) * | 1980-09-20 | 1984-11-27 | Sandoz Ltd. | Aromatic oxamides useful as stabilizers |
US4572807A (en) * | 1981-03-21 | 1986-02-25 | Henkel Kommanditgesellschaft Auf Aktien | Oligophosphonic acids, oligophosphinic acids, and process of preparation |
US4412024A (en) * | 1981-09-14 | 1983-10-25 | Sandoz Ltd. | Concentrated solutions of aromatic oxamide stabilizers |
US4489186A (en) * | 1982-07-05 | 1984-12-18 | Mitsubishi Gas Chemical Company, Inc. | Polyphenylene ether resin composition |
US4920169A (en) * | 1986-12-02 | 1990-04-24 | Sandoz Ltd. | Oxalic acid di(phenylamides) and use thereof as UV absorbers |
US4833038A (en) * | 1988-03-14 | 1989-05-23 | Ppg Industries, Inc. | UV curable coatings containing oxalanilide stabilizers, method of curing, and coated substrates therefrom |
US4921726A (en) * | 1988-03-14 | 1990-05-01 | Ppg Industries, Inc. | UV curable coatings containing oxalanilide stabilizers, method of curing, and coated substrates therefrom |
US5716667A (en) * | 1994-12-01 | 1998-02-10 | Kansai Paint Co., Ltd. | Method of temporarily protecting finished coating film on automobile body |
FR2735139A1 (en) * | 1995-06-07 | 1996-12-13 | Clariant Finance Bvi Ltd | COATING COMPOSITION COMPRISING A FILM-FORMING POLYMER AND A STABILIZING POLYMER COMPOSITION |
US5821288A (en) * | 1995-06-07 | 1998-10-13 | Clariant Finance (Bvi) Limited | Organic compounds |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3808273A (en) | Process for the production of alkylated n,n'-diphenyloxamides | |
US3529982A (en) | Process for protecting organic material from the action of ultraviolet rays | |
US3249608A (en) | Hydroxyphenyl-1, 3, 5-triazines | |
US4085062A (en) | N,N'-bis-aromaticformamidines useful as sunscreening agents | |
US3769294A (en) | 2-(2'-hydroxy-5'-octylphenyl) naphthotriazole | |
EP0743309B1 (en) | o-Hydroxyphenyl-s-triazines as UV stabilisers | |
EP0654469B1 (en) | Stabilised polymers containing o-hydroxyphenyl-s-triazines | |
CA1077046A (en) | Branched chain dodecyl isomeric mixtures of 2-(5'-dodecyl-2'-hydroxyphenyl) benzotriazole as stabilizers for heat and light sensitive materials | |
CN101010369B (en) | Stabilization of organic materials | |
US3215725A (en) | Bis-alpha-cyano-beta, beta-diphenylacrylic acid derivatives | |
EP0415887B1 (en) | 3-Phenyl-benzofuran-3-ones | |
US3906033A (en) | Oxalic acid diarylamides | |
US3542573A (en) | Use of oxalic acid diarylamides as light filters | |
KR19990063827A (en) | New cinnamic amides and their use as stabilizers | |
US3511804A (en) | Protection of organic materials from ultraviolet radiation | |
US4003875A (en) | Asymmetrical oxalic acid diaryl amide stabilizers | |
US5332568A (en) | S-triazine derivatives having light-protecting action | |
US3683020A (en) | Bis-oxalic acid diamides for use as stabilizers | |
US3049509A (en) | Heterocyclic ultraviolet absorbers | |
US3160665A (en) | Hydroxy-benzophenones | |
US3936418A (en) | Benzotriazole ortho-ester ultraviolet stabilizers and their use in organic compositions | |
US3573216A (en) | Heterocyanoacrylate u.v. absorbers | |
US3413263A (en) | Alkylphenone stabilizers, stabilized compositions and methods for making same | |
US3379677A (en) | Ultraviolet light stabilizers for plastic materials | |
US2910454A (en) | Hydrocarbon polymers stabilized with b-resorcylic acid diesters |